Multilayer membranes, separators, batteries, and methods

Abstract

In accordance with at least selected embodiments, the application, disclosure or invention relates to improved membranes, separator membranes, separators, battery separators, secondary lithium battery separators, multilayer membranes, multilayer separator membranes, multilayer separators, multilayer battery separators, multilayer secondary lithium battery separators, multilayer battery separators, electrochemical cells, batteries, capacitors, super capacitors, double layer super capacitors, fuel cells, lithium batteries, lithium ion batteries, secondary lithium batteries, and/or secondary lithium ion batteries, and/or methods for making and/or using such membranes, separator membranes, separators, battery separators, secondary lithium battery separators, electrochemical cells, batteries, capacitors, fuel cells, lithium batteries, lithium ion batteries, secondary lithium batteries, and/or secondary lithium ion batteries, and/or devices, vehicles or products including the same, and/or the like.

1 - 59 . (canceled) 
     
     
         60 . A microporous membrane comprising:
 two outer layers, each outer layer comprising a polyolefin; and   a plurality of inner layers, each inner layer comprising a polyolefin;   
       wherein each of the outer layers is laminated to an inner layer and each of the plurality of inner layers is laminated to at least one other inner layer. 
     
     
         61 . The microporous membrane of  claim 60 , wherein the each of the outer layers comprises a polypropylene, a polypropylene blend, a polypropylene copolymer, a polyethylene, a polyethylene blend, a polyethylene copolymer, or any combination thereof. 
     
     
         62 . The microporous membrane of  claim 60 , wherein each outer layer comprises a polypropylene, a polypropylene blend, a polypropylene copolymer, or any combination thereof. 
     
     
         63 . The microporous membrane of  claim 60 , wherein the each of the plurality of inner layers comprises a polypropylene, a polypropylene blend, a polypropylene copolymer, a polyethylene, a polyethylene blend, a polyethylene copolymer, or any combination thereof. 
     
     
         64 . The microporous membrane of  claim 60 , wherein there are two, three, four, five, six or more inner layers. 
     
     
         65 . The microporous membrane of  claim 60 , wherein there are three inner layers. 
     
     
         66 . The microporous membrane of  claim 60 , wherein microporous membrane is a penta-layered membrane comprising a first outer layer, a first inner layer, a second inner (or middle) layer, a third inner layer, and a second outer layer. 
     
     
         67 . The microporous membrane of  claim 66 , wherein
 the first outer layer is laminated to the first inner layer;   the first inner layer is laminated to the first outer layer and the second inner (or middle) layer;   the second inner (or middle) layer is laminated to the first inner layer and the third inner layer;   and the third inner is laminated to the second inner (or middle) layer and the second outer layer.   
     
     
         68 . The microporous membrane of  claim 66 , wherein the first and second outer layers and the second inner (or middle) layer comprise a polypropylene, a polypropylene blend, a polypropylene copolymer, or any combination thereof. 
     
     
         69 . The microporous membrane of  claim 68 , wherein the first and third inner layers comprise a polyethylene, a polyethylene blend, a polyethylene copolymer, or any combination thereof. 
     
     
         70 . The microporous membrane of  claim 60 , wherein the microporous membrane comprises a penta-layered membrane comprising a structure of PP/PE/PP/PE/PP, where PP is a polypropylene, a polypropylene blend, a polypropylene copolymer, or any combination thereof, and PE is a polyethylene, a polyethylene blend, a polyethylene copolymer, or any combination thereof. 
     
     
         71 . The microporous membrane of  claim 70 , wherein each of the five layers (inner or outer) of the penta-layered membrane is laminated to their respective adjacent layers (inner or outer). 
     
     
         72 . The microporous membrane of  claim 60 , wherein:
 each layer (inner or outer) comprises two, three, four, five, or more sublayers.   each layer (inner or outer) comprises two, three, or more sublayers;   each layer (inner or outer) comprises three sublayers;   each layer (inner or outer) comprises three sublayers, wherein each sublayer has a maximum average thickness of 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1 □m or less;   the membrane has a maximum average thickness ranging from 1 to 50 microns   each layer comprises a maximum average thickness of 33%, 32%, 31%, 30%, 29%, 28%, or less that 28% of a total average thickness of the membrane;   the membrane has been machine direction stretched;   the membrane has been transverse direction stretched;   the membrane has been machine direction stretched and transverse direction stretched;   the microporous membrane has been transverse direction stretched and calendered;   the membrane further comprises an additive;   the membrane further comprises an additive, wherein the additive comprises a functionalized polymer, an ionomer, a cellulose nanofiber, an inorganic particle, a lubricating agent, a nucleating agent, a cavitation promoter, a fluoropolymer, a cross-linker, a x-ray detectable material, a polymer processing agent, a high temperature melt index (NTMI) polymer, an electrolyte additive, an energy dissipative non-miscible additive, or any combination thereof; or   the membrane comprises an additive, wherein the additive is a coating on the first outer layer, the second outer layer, or both the first and second layers.   
     
     
         73 . The microporous membrane of  claim 72 , wherein each of the sublayers is coextruded, an optionally wherein each layer has a maximum average thickness of 1.2 mil or less, 1.1 mil or less, 1 mil or less, or 0.9 mil or less 0.8 mil or less, 0.75 mil or less, 0.5 mil or less, 0.4 mil or less, 0.3 mil or less, or 0.2 mil or less prior to stretching. 
     
     
         74 . The microporous membrane of  claim 68 , wherein: the first and second outer layers and the second inner (or middle) layer have an average polypropylene pore size in the range of 0.02 and 0.06 μm; or
 the first and third inner layers have an average polyethylene pore size in the range of 0.03 to 1.0 μm. 
 
     
     
         75 . The microporous membrane of  claim 60 , wherein:
 the membrane has an increased or improved elasticity at or above 150° C. compared to a PP/PE/PP tri-layer microporous membrane having the same thickness, Gurley, porosity, and/or layer composition make-up as the membrane;   the membrane has an increased or improved puncture resistance compared to a PP/PE/PP tri-layer microporous membrane having the same thickness, Gurley, porosity, and/or layer composition make-up as the membrane;   the membrane has an increased or improved machine direction tensile at break compared to a PP/PE/PP tri-layer microporous membrane having the same thickness, Gurley, porosity, and/or layer composition make-up as the membrane; or   the membrane has an increased or improved TD elongation compared to a PP/PE/PP tri-layer microporous membrane having the same thickness, Gurley, porosity, and/or layer composition make-up as the membrane.   
     
     
         76 . In a lithium ion battery, a device, or a textile, the improvement comprising the microporous membrane of  claim 60 . 
     
     
         77 . A method of making a multilayer microporous membrane, the method comprising:
 extruding a polypropylene precursor comprising a plurality of sublayers;   extruding a polyethylene precursor comprising a plurality of sublayers;   laminating the extruded polypropylene precursor layers with the extruded polyethylene precursor layers to form a first intermediate precursor having an alternating polyethylene and polypropylene precursors structure;   simultaneously or singly laminating a first outer layer comprising one of the extruded polypropylene precursors to a first surface of the intermediate precursor and a second outer layer comprising one of the extruded polypropylene precursors to a second surface of the first intermediate precursor opposite the first surface to form a second intermediate precursor;   annealing the second intermediate precursor to form an annealed multilayer membrane;   stretching the annealed multilayer membrane to form a microporous multilayer membrane, wherein the stretching is uniaxial or biaxial; and   optionally calendering the microporous multilayer membrane.   
     
     
         78 . The method of  claim 77 , wherein:
 the first intermediate precursor comprises a trilayer structure of PE/PP/PE or PP/PE/PP or a four-layer structure of PP/PE/PE/PP or PE/PP/PP/PE;   the second intermediate precursor comprises a penta-layer structure of PP/PE/PP/PE/PP or PE/PP/PE/PP/PE or a six-layer structure of PP/PP/PE/PE/PP/PP, PE/PE/PP/PP/PE/PE, PP/PE/PE/PE/PE/PP, or PE/PP/PP/PP/PP/PE;   the uniaxial stretching is in the machine direction or the transverse direction;   the biaxial stretching is in the machine direction and transverse direction;   the biaxial stretching is in the machine direction and transverse direction, wherein the machine direction and transverse direction stretching is sequential or simultaneous;   the extruded polypropylene precursor comprises two, three, four, or more sublayers;   the extruded polyethylene precursor comprises two, three, four, or more sublayers;   the second intermediate precursor comprises a penta-layer structure of PP/PE/PP/PE/PP, where each of the polyethylene and polypropylene precursors comprises three sublayers; or   the extruded polypropylene precursor and the extruded polyethylene precursor are nonporous.   
     
     
         79 . The method of  claim 78 , further comprising the step of coating one or more of the first outer layer and the second outer layer. 
     
     
         80 . A method for making a penta-layer microporous membrane comprising:
 extruding a plurality of polypropylene membranes and polyethylene membranes;   laminating one of the polyethylene membranes to a first side of a polypropylene membrane and another one of the polyethylene membranes to an opposite second side of the polypropylene membrane to form an inverted trilayer membrane having a structure of PE/PP/PE;   simultaneously or singly laminating one of the polypropylene layers to one of the polyethylene membranes in the inverted trilayer membrane and another of the polypropylene layers to the other polyethylene membrane in the inverted trilayer membrane to form a penta-layer membrane having a structure of PP/PE/PP/PE/PP;   annealing the penta-layer membrane; and   stretching the annealed penta-layer membrane to form the microporous membrane, wherein the stretching is uniaxial or biaxial or stretching and optionally calendering the annealed penta-layer membrane to form the microporous multilayer membrane.   
     
     
         81 . A battery separator, a lithium ion battery separator, a device, or a textile comprising the microporous membrane formed by the method of  claim 78 . 
     
     
         82 . A multilayer microporous membrane comprising three or more lamination interfaces and exhibiting a puncture strength of 150 g or more 260 g or more, 270 g or more, 280 g or more, 290 g or more, 300 g or more, 310 g or more, 400 g or more, or 500 g or more. 
     
     
         83 . The membrane of  claim 82 , comprising three lamination interfaces; comprising four lamination surfaces; or comprising five or more lamination surfaces. 
     
     
         84 . The membrane of  claim 82 , wherein the membrane comprises four or more layers, each layer comprising two or more sublayers formed by a co-extrusion process. 
     
     
         85 . In a electrochemical cell, battery, capacitor, super capacitor, double layer super capacitor, fuel cell, lithium battery, lithium ion battery, secondary lithium battery, and/or secondary lithium ion battery the improvement comprising the microporous membrane of  claim 60 .